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Publications (10 of 96) Show all publications
Andersson, E. K. W., Wu, L.-T., Bertoli, L., Weng, Y.-C., Friesen, D., Elbouazzaoui, K., . . . Hahlin, M. (2024). Initial SEI formation in LiBOB-, LiDFOB- and LiBF4-containing PEO electrolytes. Journal of Materials Chemistry A, 12(15), 9184-9199
Open this publication in new window or tab >>Initial SEI formation in LiBOB-, LiDFOB- and LiBF4-containing PEO electrolytes
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2024 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 12, no 15, p. 9184-9199Article in journal (Refereed) Published
Abstract [en]

A limiting factor for solid polymer electrolyte (SPE)-based Li-batteries is the functionality of the electrolyte decomposition layer that is spontaneously formed at the Li metal anode. A deeper understanding of this layer will facilitate its improvement. This study investigates three SPEs – polyethylene oxide:lithium tetrafluoroborate (PEO:LiBF4), polyethylene oxide:lithium bis(oxalate)borate (PEO:LiBOB), and polyethylene oxide:lithium difluoro(oxalato)borate (PEO:LiDFOB) – using a combination of electrochemical impedance spectroscopy (EIS), galvanostatic cycling, in situ Li deposition photoelectron spectroscopy (PES), and ab initio molecular dynamics (AIMD) simulations. Through this combination, the cell performance of PEO:LiDFOB can be connected to the initial SPE decomposition at the anode interface. It is found that PEO:LiDFOB had the highest capacity retention, which is correlated to having the least decomposition at the interface. This indicates that the lower SPE decomposition at the interface still creates a more effective decomposition layer, which is capable of preventing further electrolyte decomposition. Moreover, the PES results indicate formation of polyethylene in the SEI in cells based on PEO electrolytes. This is supported by AIMD that shows a polyethylene formation pathway through free-radical polymerization of ethylene.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2024
National Category
Materials Chemistry Physical Chemistry Polymer Technologies
Identifiers
urn:nbn:se:uu:diva-528371 (URN)10.1039/d3ta07175h (DOI)001187317000001 ()38633215 (PubMedID)
Funder
StandUpSwedish Foundation for Strategic Research, 139501338EU, Horizon 2020, 860403EU, Horizon 2020, 772777Swedish Energy Agency, P2021-90225
Available from: 2024-05-21 Created: 2024-05-21 Last updated: 2024-05-21Bibliographically approved
Jeschull, F., Hub, C., Kolesnikov, T. I., Sundermann, D., Hernández, G., Voll, D., . . . Théato, P. (2024). Multivalent Cation Transport in Polymer Electrolytes: Reflections on an Old Problem. Advanced Energy Materials, 14(4), Article ID 2302745.
Open this publication in new window or tab >>Multivalent Cation Transport in Polymer Electrolytes: Reflections on an Old Problem
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2024 (English)In: Advanced Energy Materials, ISSN 1614-6832, E-ISSN 1614-6840, Vol. 14, no 4, article id 2302745Article in journal, Editorial material (Refereed) Published
Abstract [en]

Today an unprecedented diversification is witnessed in battery technologies towards so-called post-Li batteries, which include both other monovalent (Na+ or K+) and multivalent ions (e.g., Mg2+ or Ca2+). This development is driven, among other factors, by goals to establish more sustainable and cheaper raw material platforms, using more abundant raw material, while maintaining high energy densities. For these new technologies a decisive role falls to the electrolyte, that ultimately needs to form stable electrode-electrolyte interfaces and provide sufficient ionic conductivity, while guaranteeing high safety. The transport of metal-ions in a polymer matrix is studied extensively as solid electrolytes for battery applications, particularly for Li-ion batteries and are now also considered for multivalent systems. This poses a great challenge as ion transport in the solid becomes increasingly difficult for multivalent ions. Interestingly, this topic is a subject of interest for many years in the 80s and 90s and many of the problems then are still causing issues today. Owing to recent progress in this field new possibilities arise for multivalent ion transport in solid polymer electrolytes. For this reason, in this perspective a stroll down memory lane is taken, discuss current advancements and dare a peek into the future.

Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2024
Keywords
calcium-batteries, magnesium-batteries, multivalent, solid polymer electrolyte (SPE), solid-state batteries
National Category
Materials Chemistry Other Chemical Engineering
Identifiers
urn:nbn:se:uu:diva-531366 (URN)10.1002/aenm.202302745 (DOI)001117887900001 ()
Funder
German Research Foundation (DFG), 390874152
Available from: 2024-06-14 Created: 2024-06-14 Last updated: 2024-06-14Bibliographically approved
Gogoi, N., Wahyudi, W., Mindemark, J., Hernández, G., Broqvist, P. & Berg, E. (2024). Reactivity of Organosilicon Additives with Water in Li-ion Batteries. The Journal of Physical Chemistry C, 128(4), 1654-1662
Open this publication in new window or tab >>Reactivity of Organosilicon Additives with Water in Li-ion Batteries
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2024 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 128, no 4, p. 1654-1662Article in journal (Refereed) Published
Abstract [en]

Introducing small volumes of organosilicon-containing additives as part of lithium-ion battery (LIB) electrolyte engineering has been getting a lot of attention owing to these additives’ multifunctional properties. Tris(trimethylsilyl)phosphate (TMSPa) is a prominent member of this class of additives and scavenges Lewis bases such as water, although the rate at which the reaction occurs and the fate of the resultant product in the battery system still remain unknown. Herein, we have employed complementary nuclear magnetic resonance and gas chromatography–mass spectrometry to systematically study the reactivity of TMSPa with water in conventional organic carbonate solvents mimicking the Li-ion cell environment. The reaction products are identified, and a working reaction pathway is proposed by following the chemical evolution of the products over varying time and temperatures. We found that the main reaction products are trimethylsilanol (TMSOH) and phosphoric acid (H3PO4); however, various P–O–Si-containing intermediates were also found. Similar to water, the Lewis base TMSOH can undergo reaction with TMSPa at room temperature to form hexamethyldisiloxane and can also activate ethylene carbonate (EC) ring-opening reactions at elevated temperatures (≥80 °C), yielding a TMS derivative with ethylene glycol (TMS-EG). While the formation of TMS-EG at the expense of EC is in principle an unwanted parasitic reaction, it should be noted that this reaction is only activated at elevated temperatures in comparison to EC ring-opening by H2O, which takes place at ≥40 °C. Thus, the study underlines the advantages of organo-silicon compounds as electrolyte additives. Elucidating the reaction mechanism in model systems like this is important for future studies of similar additives in order to improve the accuracy of additive exploration in LIBs.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-522242 (URN)10.1021/acs.jpcc.3c07505 (DOI)001156038200001 ()
Funder
Swedish Research Council, 2016-04069Knut and Alice Wallenberg Foundation, 2017.0204Swedish Foundation for Strategic Research, FFL18-0269
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-06Bibliographically approved
Weng, Y.-C., Andersson, R., Lee, M.-T., Mindemark, J., Lindblad, A., Hahlin, M. & Hernández, G. (2024). Spatially and Chemically Resolved Degradation of Fluorine-Free Electrolyte on Silicon/Graphite Surfaces. Journal of the Electrochemical Society, 171(6), Article ID 060527.
Open this publication in new window or tab >>Spatially and Chemically Resolved Degradation of Fluorine-Free Electrolyte on Silicon/Graphite Surfaces
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2024 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 171, no 6, article id 060527Article in journal (Refereed) Published
Abstract [en]

Implementation of fluorine-free electrolytes that are safer and more sustainable than the state-of-the-art highly fluorinated electrolytes requires a thorough understanding of the interphase formation process. This work investigates the effects of LiPF6- and lithium bis(oxalato)borate (LiBOB)-based electrolytes on the electrochemical performance and surface chemistry of graphite, silicon, and silicon-graphite composite electrodes. The LiBOB-based electrolyte degrades more with the presence of silicon in the electrode, and tends to form a thicker solid electrolyte interphase (SEI) layer compared to the LiPF6-based electrolyte. Different degradation distributions were also found in the graphite-silicon composite electrode: The LiPF6 degradation products tend to form on silicon, while the LiBOB degradation products preferentially form on carbon species. These results provide insights into the relationship between electrolytes and electrodes in terms of electrochemical performance, as well as SEI composition and morphology.

Place, publisher, year, edition, pages
Electrochemical Society, 2024
National Category
Condensed Matter Physics Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-533655 (URN)10.1149/1945-7111/ad5621 (DOI)001250756600001 ()
Funder
EU, Horizon 2020, 875514Swedish Energy Agency, 40466-1StandUpSwedish Energy Agency, P2021-90225
Available from: 2024-06-27 Created: 2024-06-27 Last updated: 2024-07-04Bibliographically approved
Nkosi, F. P., Cuevas, I., Valvo, M., Mindemark, J., Mahun, A., Abbrent, S., . . . Edström, K. (2024). Understanding Lithium-Ion Conductivity in NASICON-Type Polymer-in-Ceramic Composite Electrolytes. ACS Applied Energy Materials, 7(10), 4609-4619
Open this publication in new window or tab >>Understanding Lithium-Ion Conductivity in NASICON-Type Polymer-in-Ceramic Composite Electrolytes
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2024 (English)In: ACS Applied Energy Materials, E-ISSN 2574-0962, Vol. 7, no 10, p. 4609-4619Article in journal (Refereed) Published
Abstract [en]

Composite electrolytes comprising distinctive polyether (PEO) or polyester (PCL, P(CL-co-TMC)) polymers in combination with a high loading of Li1.4Al0.4Ti1.6(PO4)3 NASICON-type ceramic powders (LATP, 70 wt %) are investigated to gain insights into the limitations of their ion conductivity in resulting polymer-in-ceramic solid-state electrolyte systems. Here, LATP constitutes an advantageous ceramic Li-ion conductor with fair ionic conductivity that does not immediately suffer from limitations arising from interface issues due to the detrimental formation of surface species (e.g., Li2CO3) in contact with air and/or surrounding polymers. The Li-ion transport in all these composite electrolytes is found to follow a slow-motion regime in the polymer matrix, regardless of the nature of the polymer used. Interestingly, the weakly Li-coordinating polyester-based polymers PCL and P(CL-co-TMC) exhibit an exchange of Li+ ions between the polymer and ceramic phases and high Li-ion transference numbers compared to the polyether PEO matrix, which has strong Li–polymer coordination. LATP particle agglomeration is nevertheless observed in all the composite electrolytes, and this most likely represents a dominating cause for the lower Li-ion conductivity values of these composites when compared to those of their solid polymer electrolyte (SPE) counterparts. These findings add another step toward the development of functional composite electrolytes for all-solid-state batteries.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
Keywords
Li1+xAlxTi2−x(PO4)3, All-solid-state batteries, Polyether and polyester polymers Li-ion coordination properties Interfacial Li-ion transport
National Category
Other Electrical Engineering, Electronic Engineering, Information Engineering Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-531308 (URN)10.1021/acsaem.4c00701 (DOI)001225265200001 ()
Funder
Swedish Energy Agency, 2017-013571VinnovaStandUp
Available from: 2024-06-12 Created: 2024-06-12 Last updated: 2024-06-13Bibliographically approved
Vijayakumar, V., Ghosh, M., Asokan, K., Sukumaran, S. B., Kurungot, S., Mindemark, J., . . . Nair, J. R. (2023). 2D Layered Nanomaterials as Fillers in Polymer Composite Electrolytes for Lithium Batteries. Advanced Energy Materials, 13(15), Article ID 2203326.
Open this publication in new window or tab >>2D Layered Nanomaterials as Fillers in Polymer Composite Electrolytes for Lithium Batteries
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2023 (English)In: Advanced Energy Materials, ISSN 1614-6832, E-ISSN 1614-6840, Vol. 13, no 15, article id 2203326Article, review/survey (Refereed) Published
Abstract [en]

Polymer composite electrolytes (PCEs), i.e., materials combining the disciplines of polymer chemistry, inorganic chemistry, and electrochemistry, have received tremendous attention within academia and industry for lithium-based battery applications. While PCEs often comprise 3D micro- or nanoparticles, this review thoroughly summarizes the prospects of 2D layered inorganic, organic, and hybrid nanomaterials as active (ion conductive) or passive (nonion conductive) fillers in PCEs. The synthetic inorganic nanofillers covered here include graphene oxide, boron nitride, transition metal chalcogenides, phosphorene, and MXenes. Furthermore, the use of naturally occurring 2D layered clay minerals, such as layered double hydroxides and silicates, in PCEs is also thoroughly detailed considering their impact on battery cell performance. Despite the dominance of 2D layered inorganic materials, their organic and hybrid counterparts, such as 2D covalent organic frameworks and 2D metal-organic frameworks are also identified as tuneable nanofillers for use in PCE. Hence, this review gives an overview of the plethora of options available for the selective development of both the 2D layered nanofillers and resulting PCEs, which can revolutionize the field of polymer-based solid-state electrolytes and their implementation in lithium and post-lithium batteries.

Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2023
Keywords
2D materials, clay minerals, covalent organic frameworks, metal-organic frameworks, MXene, polymer composite electrolyte, solid-state batteries
National Category
Materials Chemistry Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-513060 (URN)10.1002/aenm.202203326 (DOI)000947031300001 ()
Funder
EU, European Research CouncilStandUp
Available from: 2023-10-16 Created: 2023-10-16 Last updated: 2023-10-16Bibliographically approved
Wu, L.-T., Andersson, E. K. W., Hahlin, M., Mindemark, J., Brandell, D. & Jiang, J.-C. (2023). A method for modelling polymer electrolyte decomposition during the Li-nucleation process in Li-metal batteries. Scientific Reports, 13(1), Article ID 9060.
Open this publication in new window or tab >>A method for modelling polymer electrolyte decomposition during the Li-nucleation process in Li-metal batteries
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2023 (English)In: Scientific Reports, E-ISSN 2045-2322, Vol. 13, no 1, article id 9060Article in journal (Refereed) Published
Abstract [en]

Elucidating the complex degradation pathways and formed decomposition products of the electrolytes in Li-metal batteries remains challenging. So far, computational studies have been dominated by studying the reactions at inert Li-metal surfaces. In contrast, this study combines DFT and AIMD calculations to explore the Li-nucleation process for studying interfacial reactions during Li-plating by introducing Li-atoms close to the metal surface. These Li-atoms were added into the PEO polymer electrolytes in three stages to simulate the spontaneous reactions. It is found that the highly reactive Li-atoms added during the simulated nucleation contribute to PEO decomposition, and the resulting SEI components in this calculation include lithium alkoxide, ethylene, and lithium ethylene complexes. Meanwhile, the analysis of atomic charge provides a reliable guideline for XPS spectrum fitting in these complicated multicomponent systems. This work gives new insights into the Li-nucleation process, and experimental XPS data supporting this computational strategy. The AIMD/DFT approach combined with surface XPS spectra can thus help efficiently screen potential polymer materials for solid-state battery polymer electrolytes.

Place, publisher, year, edition, pages
Springer Nature, 2023
National Category
Materials Chemistry Physical Chemistry Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-506908 (URN)10.1038/s41598-023-36271-5 (DOI)001000764200001 ()37271770 (PubMedID)
Funder
Swedish Foundation for Strategic Research, ST19-0095StandUp
Available from: 2023-07-03 Created: 2023-07-03 Last updated: 2023-07-03Bibliographically approved
Bertoli, L., Bloch, S., Andersson, E., Magagnin, L., Brandell, D. & Mindemark, J. (2023). Combination of solid polymer electrolytes and lithiophilic zinc for improved plating/stripping efficiency in anode-free lithium metal solid-state batteries. Electrochimica Acta, 464, Article ID 142874.
Open this publication in new window or tab >>Combination of solid polymer electrolytes and lithiophilic zinc for improved plating/stripping efficiency in anode-free lithium metal solid-state batteries
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2023 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 464, article id 142874Article in journal (Refereed) Published
Abstract [en]

Anode-free lithium metal batteries and solid-state batteries represent some of the most promising alternatives to the current Li-ion technology. The possibility to reach high energy density, due to the exploitation of Li-metal plating/stripping and the elimination of excess anode material, motivate the interest at both academic and in-dustrial levels. Despite these favourable properties, the use of Li-metal has always been extremely challenging and inefficient. This becomes particularly relevant in anode-free systems where no excess of lithium is introduced in the cell. The efficiency and quality of the deposition process is therefore of utmost importance. To optimize the Li-metal plating process, a combination of solid polymer electrolytes and a lithiophilic metal is applied herein, using in situ deposition of a zinc interlayer from a PEO-based SPE to modify the Cu current collector. Im-provements in specific capacity, coulombic efficiency and cyclability with the addition of zinc as lithiophilic metal is verified in full anode-free solid-state Li-batteries, while plating/stripping in half-cell configuration provides additional insights into the relevant mechanisms. The exploitation of the in situ deposited lithiophilic layer reveals an innovative and practical optimization strategy for the future of anode-free solid-state batteries.

Place, publisher, year, edition, pages
Elsevier BV, 2023
Keywords
Anode-free batteries, Solid polymer electrolytes, Li-metal batteries, Lithiophilic metals, Zinc triflate
National Category
Materials Chemistry Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-510007 (URN)10.1016/j.electacta.2023.142874 (DOI)001047684800001 ()
Funder
Swedish Foundation for Strategic Research, 139501338EU, European Research Council, 771777StandUp
Available from: 2023-08-28 Created: 2023-08-28 Last updated: 2023-08-28Bibliographically approved
Hernández, G., Lee, T. K., Erdélyi, M., Brandell, D. & Mindemark, J. (2023). Do non-coordinating polymers function as host materials for solid polymer electrolytes?: The case of PVdF-HFP. Journal of Materials Chemistry A, 11(28), 15329-15335
Open this publication in new window or tab >>Do non-coordinating polymers function as host materials for solid polymer electrolytes?: The case of PVdF-HFP
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2023 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 11, no 28, p. 15329-15335Article in journal (Refereed) Published
Abstract [en]

In the search for novel solid polymer electrolytes (SPEs), primarily targeting battery applications, a range of different polymers is currently being explored. In this context, the non-coordinating poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) polymer is a frequently utilized system. Considering that PVdF-HFP should be a poor solvent for cation salts, it is counterintuitive that this is a functional host material for SPEs. Here, we do an in-depth study of the salt dissolution properties and ionic conductivity of PVdF-HFP-based electrolytes, using two different fabrication methods and also employing a low-molecular-weight solvent analogue. It is seen that PVdF-HFP is remarkably poor as an SPE host, despite its comparatively high dielectric constant, and that the salt dissolution properties instead are controlled by fluorophilic interactions of the anion with the polymer.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2023
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-510972 (URN)10.1039/d3ta01853a (DOI)001019430300001 ()37469657 (PubMedID)
Funder
EU, European Research Council, 771777 FUN POLYSTOREStandUp
Available from: 2023-09-06 Created: 2023-09-06 Last updated: 2023-09-06Bibliographically approved
Emilsson, S., Vijayakumar, V., Mindemark, J. & Johansson, M. (2023). Exploring the use of oligomeric carbonates as porogens and ion-conductors in phase-separated structural electrolytes for Lithium-ion batteries. Electrochimica Acta, 449, Article ID 142176.
Open this publication in new window or tab >>Exploring the use of oligomeric carbonates as porogens and ion-conductors in phase-separated structural electrolytes for Lithium-ion batteries
2023 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 449, article id 142176Article in journal (Refereed) Published
Abstract [en]

Phase-separated structural battery electrolytes (SBEs) have the potential to enhance the mechanical stability of the electrolyte while maintaining a high ion conduction. This can be achieved via polymerization-induced phase separation (PIPS), which creates a two-phase system with a liquid electrolyte percolating a mesoporous ther-moset. While previous studies have used commercially available liquid electrolytes, this study investigates the use of novel oligomeric carbonates to enhanced the safety of the SBEs. Increasing the carbonate chain length significantly enhances the thermal stability of the SBEs. Tuning the molecular structure of the liquid electrolyte has a significant effect on the PIPS process and SBE morphology. Using a combination of analyses on a series of wet and dried SBEs, the complex interplay between the phases is interpreted. When an increased pore size is achieved, it leads to a lower MacMullin number (NM). A conductivity of 2 x 10-5 S/cm with a NM=13 could be achieved, while maintaining a thermal stability up to 150 degrees C. The present study demonstrates a versatile approach to tailor this type of electrolyte.

Place, publisher, year, edition, pages
Elsevier, 2023
Keywords
Structural batteries, Polymer electrolyte, Polymerization-induced phase separation, Ionic conductivity, McMullin number, Carbonate oligomers, Lithium ion
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-500585 (URN)10.1016/j.electacta.2023.142176 (DOI)000957971600001 ()
Funder
Vinnova, 2019-00064StandUpEU, Horizon 2020, 875514
Available from: 2023-04-21 Created: 2023-04-21 Last updated: 2023-10-16Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-9862-7375

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